Reduction of the phosphorous cross-contamination in n-i-p solar cells prepared in a single-chamber PECVD reactor

A new approach to reduce phosphorous contamination in the intrinsic layer during the deposition of amorphous silicon (a-Si:H) n-i-p solar cells prepared in single-chamber reactors is presented. This novel process consists of a hydrogen etching plasma performed after the n-layer deposition, which prevents a recycling of phosphorous from the reactor walls when exposed to a hydrogen-rich plasma during the subsequent i-layer deposition. The implemented process reduces the phosphorous cross-contamination in the i-layer, as corroborated by secondary ion mass spectroscopy measurements. Furthermore, the end of the etching process can be easily monitored by measuring the DC bias voltage at the powered electrode. By applying this process, we were able to improve the fill factor from 70% up to 75%, without degradation in the other parameters of the cell, neither in the initial nor in the stabilized state. Finally, by implementing this process in a-Si:H/a-Si:H tandem solar cells we obtained an initial efficiency of 10.3% (V_oc=1.76 V, FF=74.5%, J_sc=7.8 mA cm⁻²); light soaking test resulted in a stabilized efficiency of 8.5%.     

Fabricating high performance a-Si solar cells by alternately repeating deposition and hydrogen plasma treatment method

The performance of a p-i buffer layer in pin amorphous silicon solar cell was improved by the “alternately repeating deposition and hydrogen plasma treatment method (ADHT)”. The optical bandgap of the a-Si film was increased by hydrogen plasma treatement. The wide optical bandgap and the high photoconductive a-Si:H films without carbon could be fabricated by the ADHT method. The conversion efficiency of the solar cell with a-Si:H buffer layer was almost the same as that using an a-SiC:H buffer layer. Second, the a-Si (ADHT) films were applied to the n-i buffer layer. The insertion of a-Si (ADHT) films between the i-layer and the n-layer was effective to improve the cell performance, especially the fill factor. With the use of high performance a-Si p-i and n-i buffer layer deposited by ADHT method, a cell conversion efficiency of 12.9% was obtained.     

Effects of grain boundaries on cell performance of poly-silicon thin film solar cells by 2-D simulation

The effect of grain boundaries on the performance of poly-Si thin film solar cells was studied theoretically using a 2-D simulation assuming the presence of either rectangular-shaped or graded width grain boundaries in the i-layer of p/i/n structure of solar cells. The grain boundary had an adverse effect mainly on V_oc. J_sc gradually increased and saturated with increasing solar cell thickness in cells without grain boundaries, whereas it reached a maximum for an i-layer thickness of 5 μm in polycrystalline silicon cells. The calculation using the graded width model showed that the efficiency of the p⁺/p⁻/n⁺ structure was better than that of the p⁺/n⁻/n⁺ structure. A slight p-type doping of the i-layer was found to be effective in improving cell performance.     

Performance of double junction a-Si solar cells by using ZnO:Al films with different electrical and optical properties at the n/metal interface

High-quality ZnO:Al films have been prepared by using RF-magnetron-sputtering method with resistivity ranging from 10⁻¹ to 10⁻⁴ Ω cm and transmittance above 90% in visible region. We have fabricated small area (1 cm²) double junction (a-Si/a-Si) solar cells using ZnO/Al and ZnO/Ag as back contact. The conversion efficiency of double junction a-Si solar cell increases from 9.9% to 10.9% by using ZnO/Al back contact and to 11.4% by using ZnO/Ag as back contact. Effect of variation of thickness of i-layer on performance of the cell has also been studied.     

Apparent “gettering” of the Staebler-Wronski effect in amorphous silicon solar cells

The stability behaviour of intrinsic amorphous silicon materials incorporated in a p⁺-i-n⁺ solar cell structure is considerably different from that observed by electrical characterization methods in individual thin films. This is due to the fundamental difference in Fermi-level position in a single layer compared to the situation occuring in devices. We have employed the differences in the re-equilibration behaviour that have been observed in various intrinsic materials when the Fermi-level is shifted towards the valence band edge, in order to design a cell with a new profiled i-layer which would possess an improved electric field distribution after light soaking compared to cells with a constant i-layer. The contribution of the interface region to the stabilized conversion efficiency is greatly improved, whereas the first 50 nm of the cell structure remain unchanged. Thus, it appears that the Staebler-Wronski effect is gettered away from the junction, much like the impurity gettering concept in crystalline solar cells.     

Heterogeneous growth of microcrystalline silicon germanium

Microcrystalline silicon germanium films showing excellent opto-electronic properties have been prepared at a substrate temperature of 195°C by radio frequency plasma enhanced chemical vapor deposition at 13.56 MHz. A white light (AM 1.5) photoconductivity of 5×10⁻⁵/Ω cm and ambipolar diffusion length of 114 nm (from SSPG) established the device quality. Films are intrinsic (Fermi level near midgap; activation energy E_a (0.49 eV) is approximately half the band gap (1.01 eV)). Performance of preliminary n–i–p solar cells (with μc-SiGe:H i-layer) on stainless steel and molybdenum substrates justify their photosensitivities. A current density of 9.44 mA/cm² has been generated in an i-layer of only 150 nm thick without any back-reflector. A deposition rate of 0.75 Å/s for such a thin layer gives this material much advantage than a μc-Si cell, where a thickness of >2 μm is needed. A high V_oc of 0.43 eV has been achieved for such a low mobility gap cell (Ge fraction 60%).     

High-Ts amorphous top cells for increased top cell currents in micromorph tandem cells

In the present paper, the authors discuss the application of amorphous p–i–n solar cells containing i-layers which are deposited at high substrate temperatures as top cells in amorphous silicon/microcrystalline silicon tandem (“micromorph”) solar cells. Increasing the substrate temperature for the deposition of intrinsic a-Si : H results in a reduced optical gap. The optical absorption is enhanced and thereby the current generation. A high-current generation within a relatively thin amorphous top cell is very interesting in the context of micromorph tandem cells, where the amorphous top cell should contribute a current of at least 13 mA/cm² for a total cell current density of 26 mA/cm². A detailed study of the intrinsic material deposited by VHF-GD at 70 MHz at substrate temperatures between 220°C and 360°C is presented, including samples deposited from hydrogen-diluted silane plasmas. The stability of the films against light soaking is investigated employing the μ₀τ₀ parameter, which has been shown to be directly correlated to the cell performance. The paper discusses in detail the technological problems arising from the insertion of i-layers deposited at high substrate temperatures into solar cells. These problems are specially pronounced in the case of cells in the p–i–n (superstrate) structure. The authors demonstrate that an appropriate interface layer at the p/i-interface can largely reduce the detrimental effects of i-layer deposition at high temperatures. Finally, the application of such optimized high-temperature amorphous cells as top cells in micromorph tandem cells is discussed. Current densities of 13 mA/cm² in the top cell are available with a top cell i-layer thickness of only 250 nm.     

Highly reflective nanotextured sputtered silver back reflector for flexible high-efficiency n-i-p thin-film silicon solar cells

High reflectivity is essential when a metal is used as back contact and reflector in thin-film silicon solar cells. We show that thermal annealing at 150 °C improves the reflectivity of silver films deposited by sputtering at room temperature on nanotextured substrates. The annealing provokes two interlinked effects: rearrangement of the silver layer with a modification of its morphology and an increase of up to 42% in the grain size of the polycrystalline film for the preferential orientation as measured by X-ray diffraction. The main consequence of these two mechanisms is a large increase in the reflectivity of silver when measured in air. This reflectivity increase is also noticeable in devices: amorphous silicon thin-film solar cells grown on annealed silver films yield higher internal and external quantum efficiencies compared to cells grown on as-deposited silver. The morphology modification smoothes down the substrate, which is revealed by a clear increase of the open-circuit voltage and fill factor of the cells grown on top. An amorphous silicon cell with a 200 nm nominally thick i-layer fabricated on a flexible plastic substrate yielded an initial efficiency close to 10% with 15.9 mA/cm² of short-circuit current using highly reflective annealed textured silver. We also propose, for industrial purpose, the sputtering of thin silver layer (120 nm) under moderate substrate temperature (∼150 °C) to increase the layer reflectivity, which avoids lengthening of the back reflector fabrication.     

Study on diffusion barrier layer of silicon-based thin-film solar cells on polyimide substrate

ZnO and Ni films were used as the diffusion barrier layer between Al and n-type μc-Si:H for the hydrogenated amorphous silicon (a-Si:H) solar cells on polyimide (PI) substrate. The electrical, optical and uniformity properties of ZnO or Ni film influence strongly the performance and uniformity of solar cells. The uniformity of the solar cells with ZnO diffusion barrier layer degraded with the increasing thickness of ZnO film. The uniformity of solar cells with Ni diffusion barrier layer was more than 90%, which was generally better than those with ZnO film. A power-to-weight ratio of 200 W/kg was obtained for a-Si:H thin-film solar cell on PI substrate with a size of 14.8 cm².     

p-doped μc-Si:H window layers prepared by hot-wire CVD for amorphous solar cell application

We report on boron-doped μc-Si:H films prepared by hot-wire chemical vapor deposition (HWCVD) using silane as a source gas and trimethylboron (TMB) as a dopant gas and their incorporation into all-HW amorphous silicon solar cells. The dark conductivity of these films was in the range of 1–10 (Ω cm)⁻¹. The open circuit voltage V_oc of the solar cells was found to decrease from 840 mV at low hydrogen dilution H-dil=91% to 770 mV at high H-dil =97% during p-layer deposition which can be attributed to the increased crystallinity at higher H-dil and to subsequent band edge discontinuity between μc-Si:H p- and amorphous i-layer. The short circuit current density J_sc and the fill factor FF show an optimum at an intermediate H-dil and decrease for the highest H-dil. To improve the conversion efficiency and the reproducibility of the solar cells, an amorphous-like seed layer was incorporated between TCO and the bulk p-layer. The results obtained until now for amorphous solar cells with and without the seed layer are presented. The I–V parameters for the best p–i–n solar cell obtained so far are J_sc=13.95 mA/cm², V_oc=834 mV, FF=65% and η=7.6%, where the p-layers were prepared with 2% TMB. High open circuit voltages up to 847 mV could be achieved at higher TMB concentrations.     

High-efficiency drift-field thin-film silicon solar cells grown on electronically inactive substrates

A drift-field in the base region of a solar cell can enhance the effective minority-carrier diffusion length, thus increasing the long-wavelength spectral response and energy-conversion efficiency. Silicon thin-films of 20–32 μm thickness as a cell base layer were grown by liquid-phase epitaxy (LPE) on electronically inactive heavily doped p⁺⁺-type CZ silicon substrates. Growth was performed from In/Ga solutions, and in a purified Ar/4%H₂ forming gas ambient, rather than pure H₂. The Ga dopant concentration was tailored throughout the p-type film to create a drift-field in the base layer of the solar cell. An independently confirmed efficiency of 16.4% was achieved on such an LPE drift-field thin-film silicon solar cell with a total cell area of 4.11 cm². Substrate thinning, combined with light trapping which is encouraged by the textured front surface and a highly reflective aluminium rear surface, is demonstrated to improve the long-wavelength response and thus, increase cell efficiency by a factor of up to 23.7% when thinned to a total cell thickness of 30 μm.     

p-i interface engineering and i-layer control of hot-wire a-Si:H based p-i-n solar cells using in-situ ellipsometry

In this paper we report on the effect of monitoring the i-layer region near the p-i interface with the help of in-situ kinetic and spectroscopic ellipsometry on the performance of hot-wire deposited hydrogenated amorphous silicon p-i-n solar cells. It is very clearly observed that the microstructure at the p-i interface region in terms of the Si---Si bond packing density and surface roughness significantly affects the cell performance. The filament temperature, T_Fil, was the main parameter varied to control the above mentioned two properties near the p-i interface as well as in the bulk i-layer. In order to achieve significant enhancement in the cell performance we extended the idea of the “soft start”, earlier employed for the glow discharge deposited solar cells, to the hot-wire deposited i-layer. We were able to control the i-layer properties at the p-i interface and in the bulk independently and correlate these to the cell performance. It is shown that a major increase in cell performance can be achieved by improving the microstructure of the growing film directly at the p-i interface. Most interestingly, no significant deterioration in cell efficiency has been observed if only the p-i interface was properly controlled but the i-layer was of lower quality. These results are also shown to be consistent with model calculations of a numerical simulation. Our results therefore provide a clue to prepare hot-wire a-Si:H based solar cells with high efficiency and in the whole at high growth rates, which is needed for a more economic a-Si:H solar cell production.     

Influence of the layer thickness and hydrogen dilution on electrical properties of large area amorphous silicon p–i–n solar cell

The aim of this work is to present data concerning the optimization of performances of a large area amorphous silicon p–i–n solar cell (30×40 cm²) deposited by plasma enhanced chemical vapour deposition (PECVD) at 27.12 MHz. In this work the solar cell was split into small areas of 0.126 cm², aiming to study the device performance uniformity, where emphasis was put on the role of the n-layer thickness. The solar cells were studied through the spectral response behaviour in the 400–750 nm range as well as by the behaviour of the AC impedance. Solar cells with fill factor of 0.58, open circuit voltage of 0.83 V, short circuit current density of 17.14 mA/cm² and an efficiency of 8% were obtained at growth rates higher than 0.3 nm/s.     

The role of the buffer layer in the light of a new equivalent circuit for amorphous silicon solar cells

Although the beneficial effect of the buffer layer between the p- and i-layer of amorphous silicon solar cells has been known for many years, the role of this layer is controversial. This paper examines the effect of the buffer layer using a new equivalent circuit for these devices (Merten et al. IEEE Trans. Electron Dev. 45 (1988) 423–429 [1]). The parameters of this model can be easily assessed by variable illumination measurements (VIM) of the devices' I(V)-curve. With the model, collection of carriers in the bulk of the cell is easy and clearly separated from the diode behaviour of the device. The VIM-method allows for a complete analysis of the thin film cells, covering both technological and physical topics. It is shown that the dominant effect increasing the efficiency of the cells with buffer layer is the reduction of the hole injection from the p-layer which leads to a reduced diode term. The buffer layer only slightly reduces the recombination in the i-layer. This reduction mainly occurs in a region close to the p/i-interface and cannot be observed with red light (homogeneous carrier generation).     

Productivity potential of an inline deposition system for amorphous and microcrystalline silicon solar cells

Amorphous and microcrystalline silicon single layers and p-i-n solar cells were produced dynamically using an inline deposition system called “line source”. A highly uniform deposition of thin-film silicon layers with layer-thickness variations of less than ±5% was achieved. Amorphous and microcrystalline silicon single junction solar cells were dynamically fabricated with initial efficiencies of 8.3% and 6.3%, respectively. The dynamic deposition rate of these solar cells is 6.75 nm m/min in case of a-Si:H and 3.3 nm m/min for μc-Si:H. In this work it will be shown that an enhancement of the deposition rate up to 15.6 nm m/min during the i-layer deposition of a-Si:H solar cells has only a weak negative influence on the initial efficiencies of the cells. Further on, the effect of substrate velocity on solar cell characteristics of a-Si:H solar cells is investigated. Finally, a productivity estimation of the line source concept is presented.     

pin double-heterojunction thin-film solar cell p-layer assessment

The simplest realization of a pin double-heterojunction thin-film solar cell would consist of a lightly doped, moderate-bandgap absorber i-layer; a heavily doped, wide-bandgap n-layer window (cathode); and a heavily doped, wide-bandgap p-layer window (anode) in which the anode and cathode are electrically contacted by at least one transparent conductor. The focus herein is on p-layer interfacial assessment, which is accomplished using modern Schottky barrier and heterojunction theory and is directed to the analysis of p-windows for copper indium gallium diselenide (CIGS) and cadmium telluride (CdTe) thin-film solar cells. A p-type window layer serves as an electron reflector and also aids in the formation of an ohmic anode contact. Ohmic anode contacts are particularly difficult to form in CIGS and CdTe thin-film solar cells since these materials have very large ionization potentials, i.e., IP_S=5.65 (CIGS) and 5.78 V (CdTe) and significant interfacial screening, characterized by extremely small Schottky barrier interface parameters, i.e., S=0.14 (CIGS) and 0.21 (CdTe). An ideal p-type window material would be heavily doped, p-type, and would have a wide bandgap, a large ionization potential, and a smaller charge neutrality level energy than that of the absorber layer.     

Toward stabilized 10% efficiency of large-area (>5000 cm) a-Si/a-SiGe tandem solar cells using high-rate deposition

This paper reviews recent progress in large-area a-Si/a-SiGe tandem solar cells at Sanyo. Optimized hydrogen dilution conditions for high-rate deposition of hydrogenated amorphous silicon (a-Si:H) films and thinner i-layer structures have been systematically investigated for improving both the stabilized efficiency and the process throughput. As a result, a high photosensitivity of 10⁶ for a-Si:H films has been maintained up to the deposition rate of 15 Å/s. Furthermore, the world's highest initial conversion efficiency of 11.2% which corresponds to a stabilized efficiency of about 10% has been achieved for a 8252 cm² a-Si/a-SiGe tandem solar cell by combining the optimized hydrogen dilution and other successful technologies.     

Formation of a low reflective surface on crystalline silicon solar cells by chemical treatment using Ag electrodes as the catalyst

A new method was developed for making a porous silicon layer as an anti-reflective coating on the top of crystalline silicon solar cells. The porous silicon layer was formed in a mixed solution of H₂O₂ and HF by using screen-printed Ag front electrodes as the catalyst. With the help of the catalytic effect, porous silicon layers were formed by treatment in a solution chemically milder than conventional solutions. The multi-crystalline silicon solar cell covered with the porous silicon layer showed a surface reflectance below 15% in a wavelength region of 400–800 nm.     

Controlled nucleation of thin microcrystalline layers for the recombination junction in a-Si stacked cells

In high-efficiency a-Si : H based stacked cells, at least one of the two layers that form the internal n/p junction has preferentially to be microcrystalline so as to obtain sufficient recombination at the junction [1–6]. The crucial point is the nucleation of a very thin μc-Si : H layer on an amorphous (i-layer) substrate [2, 4]. In this study, fast nucleation is induced through the treatment of the amorphous substrate by a CO₂ plasma. The resulting n-layers with a high crystalline fraction were, however, found to reduce the V_oc when incorporated in tandem cells. The reduction of the V_oc could be restored only by a precise control of the crystalline fraction of the n-layer. As a technologically more feasible alternative, we propose a new, combined n-layer, consisting of a first amorphous layer for a high V_oc, and a second microcrystalline layer, induced by CO₂ treatment, for a sufficient recombination at the n/p junction. Resulting tandem cells show no V_oc losses compared to two standard single cells, and an efficient recombination of the carriers at the internal junction as proved by the low series resistance (15 Ωcm²) and the high FF ( 75%) of the stacked cells.     

Silicon thin films prepared in the transition region and their use in solar cells

Diphasic silicon films (nc-Si/a-Si:H) have been prepared by a new regime of plasma enhanced chemical vapour deposition in the region adjacent of phase transition from amorphous to microcrystalline state. Comparing to the conventional amorphous silicon (a-Si:H), the nc-Si/a-Si:H has higher photoconductivity (σ_ph), better stability, and a broader light spectral response range in the longer wavelength range. It can be found from Raman spectra that there is a notable improvement in the medium range order. The blue shift for the stretching mode and red shift for the wagging mode in the IR spectra also show the variation of the microstructure. By using this kind of film as intrinsic layer, a p–i–n junction solar cell was prepared with the initial efficiency of 8.51% and a stabilized efficiency of 8.01% (AM1.5, 100 mw/cm²) at room temperature.